Thermoplastic compositions with enhanced melt flow and compatibility

ABSTRACT

The instant invention relates to a composition of a thermoplastic polymer and a triblock-copolymer or grafted comb copolymer, with enhanced melt flow during processing. Further aspects of the invention are the triblock-copolymers or grafted comb polymers itself, a method for their production and their use as compatibilizers and meltflow enhancing additives. Yet another aspect of the invention are functional alkoxyamines, which are useful for the preparation of the triblock-copolymers or grafted comb polymers.

The instant invention relates to a composition of a thermoplasticpolymer and a triblock-copolymer or grafted comb copolymer, withenhanced melt flow during processing. Further aspects of the inventionare the triblock-copolymers or grafted comb polymers itself, a methodfor their production and their use as compatibilizers and meltflowenhancing additives. Yet another aspect of the invention are functionalalkoxyamines, which are useful for the preparation of thetriblock-copolymers or grafted comb polymers.

Productivity of formgiving and compounding processes of thermoplasticmaterials, such as extrusion or injection molding is often related tothe melt viscosity of polymers, i.e. by lowering the melt viscosity,throughput can be increased and cycle times and energy consumption canbe considerably reduced. The melt viscosity is related to the molecularweight of the polymer. Increasing the molecular weight leads to anincrease in melt viscosity.

On the other hand it is not possible to reduce the molecular weight inorder to gain a reduced melt viscosity, since other important propertiesof polymers such as mechanical strength depend also on the molecularweight of the polymer. It is therefore a clear request of the plasticand converting industry for a material combination of low melt viscosity(or enhanced melt flow) without influence on other material properties,such as mechanical strength or transparency.

Additives fulfilling at least partially the aformentioned requirementsin certain polymers are known and are often referred to as lubricants(e.g. polyethylene, polytetrafluoroethylene, amide waxes) and/orprocessing aids (fluoropolymers, silicones). However, the use of theseadditives results often in blooming, tool deposits, reduced transparencyand “fatty” surface aspect due to their inherent incompatibility withthe parent polymer.

For example U.S. Pat. No. 6,331,589 discloses diblock-copolymerscontaining one polysiloxane segment and a polystyrene or polyethylenesegment as melt flow enhancing additive.

The present invention provides a composition of a thermoplastic polymerand a triblock-copolymer, which is preferably prepared via controlledradical polymerization. The triblock-copolymer has an improvedcompatibility with the thermoplastic polymer and enhances the melt flowof the thermoplastic polymer. Mechanical properties, optical aspect,surface characteristics and color of the parent polymer are essentiallynot affected.

One aspect of the invention is a composition comprising

A) a thermoplastic polymer and

B1) a triblock-copolymer of the formula B-C-B; or

B2) a graft copolymer wherein a polymer block B is grafted onto apolymer C to form a comb copolymer of idealized formula C-B(n) wherein nis greater than 2;

wherein

the polymer block B is compatible to the thermoplastic polymer A); and

the polymer block C has a glass transition temperature of at least 20°K. below the glass transition temperature of the thermoplastic polymerA);

and the average molecular weight M_(w) of the triblock-copolymer B1) orgrafted comb copolymer B2) is below 50 000.

In general the triblock-copolymer is preferred.

The polydispersity index of the triblock-copolymer and the grafted combcopolymer is for example between 1.0 and 5.0, preferably between 1.1 and3.0 and in particular between 1.1 and 2.0.

Suitable thermoplastic polymers are mentioned below.

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VII of the Periodic Table. These metals usually have one or more        than one ligand, typically oxides, halides, alcoholates, esters,        ethers, amines, alkyls, alkenyls and/or aryls that may be either        π- or σ-coordinated. These metal complexes may be in the free        form or fixed on substrates, typically on activated magnesium        chloride, titanium(III) chloride, alumina or silicon oxide.        These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers(e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers,where the 1-olefin is generated in-situ; propylene/butadiene copolymers,isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers and their salts (ionomers) as well as terpolymers of ethylenewith propylene and a diene such as hexadiene, dicyclopentadiene orethylidene-norbornene; and mixtures of such copolymers with one anotherand with polymers mentioned In 1) above, for examplepolypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA),LLDPE/EVA, LLDPE/EM and alternating or random polyalkylene/carbonmonoxide copolymers and mixtures thereof with other polymers, forexample polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, andmixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic; where atactic polymers are preferred. Stereoblock polymers arealso included.

6a. Copolymers including aforementioned vinyl aromatic monomers andcomonomers selected from ethylene, propylene, dienes, nitriles, acids,maleic anhydrides, maleimides, vinyl acetate and vinyl chloride oracrylic derivatives and mixtures thereof, for example styrene/butadiene,styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkylmethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkylmethacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methylacrylate; mixtures of high impact strength of styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6.), especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene orα-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listed under6), for example the copolymer mixtures known as ABS, MBS, ASA or AESpolymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN) and polyhydroxybenzoates, as well as block copolyether estersderived from hydroxyl-terminated polyethers; and also polyestersmodified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

Preferably the thermoplastic polymer A is selected from the groupconsisting of polyethylene, polypropylene, polystyrene, polyacrylate,polymethacrylate, polyvinylchloride, polyphenylene-oxide,polyvinylacetate, polyamide and polyester.

In particular the thermoplastic polymer A is selected from the groupconsisting of polyethylene, polypropylene and polystyrene.

For example the polymer block C is selected from the group consisting ofpoly-n-butylacrylate, polyisoprene, polybutadiene, polyethylacrylate,and polysiloxane.

For instance the polymer block B is selected from the group consistingof polyisoprene, poly-butadiene, polystyrene polymethacrylate andpolyacrylate.

In a typical embodiment of the invention the thermoplastic polymer A andthe triblock-copolymer B-C-B are polystyrenepolystyrene-poly-n-butylacrylate-polystyrene, polystyrenepolystyrene-polyisoprene-polystyrene, polystyrenepolystyrene-polybutadiene-polystyrene, polystyrenepolystyrene-polysiloxane-polystyrene, polystyrenepolystyrene-polyethylacrylate-polystyrene, polyethylenepolyisoprene-polysiloxane-polyisoprene, polypropylenepolyisoprene-polysiloxane-polyisoprene, polymethylmethacrylatepolymethylacrylate-polysiloxane-polymethylacrylate, polyamidepolyethylacrylate-polysiloxane-polyethylacrylate, polyesterpolyethylacrylate-polysiloxane-polyethylacrylate, polyvinylchloridepolyethylacrylate-polysiloxane-polyethylacrylate, polyvinylchloridepoly-n-butylacrylate-polysiloxane-poly-n-butylacrylate,polyphenyleneoxide polystyrene-polysiloxane-polystyrene orpolyvinylacetate polymethylacrylate-polysiloxane-polymethylacrylate.

For example the glass transition temperature of the polymer block C is50° K. below the glass transition temperature of the thermoplasticpolymer A.

Preferably the average molecular weight M_(w) of the triblock-copolymeror graft-copolymer is below 30000.

Each individual block has for example an average molecular weight M_(w)of 2000 to 20000, in particular from 2000 to 10000 with the proviso thatthe total is below 50000, preferably below 30000.

Particularly the polymer block C is a polysiloxane.

Typically the triblock-copolymer or graft graft-copolymer is present inan amount of from 0.1 to 10%, preferably of from 0.5 to 5% and inparticular of from 0.5 to 3% by weight, based on the weight of thethermoplastic polymer A).

The composition may contain further additives, such as for example lightstabilizers, UV-absorbers, processing stabilizers, pigments or dyes andso on. Examples are given below.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example 2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis(3,6-di-sec-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butyl-phenol), 2,2-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzoate malonates, for exampledioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1, supplied by Uniroyal).

1.18. Ascorbic Acid (Vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenylenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylamino-methylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenyl-amino)propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyl-diphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- and dialkylatedtert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyl-oxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂—]—, whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]-benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.

2.2. 2-Hydroxybenzorphenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butylphenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxycinnamate, butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate,the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetra-methyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperldine,4-stearyloxy-2,2,6,6-tetramethyl-piperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)-malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)-ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); a condensate of 1,6-hexanediamine and2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decaneand epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,a diester of 4-methoxymethylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine,poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, areaction product of maleic acid anhydride-α-olefin copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1.3.5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thlopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,4-di-cumylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo-[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos®168, Ciba-Geigy),tris(nonylphenyl)phosphite,

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydrox-ylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenylnitrone,N-ethyl-alpha-methyinitrone, N-octyl-alpha-heptyinitrone,N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,N-hexadecyl-alpha-pentadecyinitrone,N-octadecyl-alpha-heptadecyinitrone,N-hexadecyl-alpha-heptadecylnitrone,N-ocatadecyl-alpha-pentadecylnitrone,N-heptadecyl-alpha-heptadecylnitrone,N-octadecyl-alpha-hexadecylnitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zincpyrocatecholate.

11. Nucleating agents, for example inorganic substances, such as talcum,metal oxides, such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds, such as ioniccopolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyidibenzylidene)sorbitol, and1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example plasticisers, lubricants, emulsifiers,pigments, rheology additives, catalysts, flow-control agents, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butylbenzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzo-furan-2-one,3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.

The triblock-copolymer or grafted comb copolymer of the invention andoptional further components may be added to the thermoplastic polymermaterial individually or mixed with one another. If desired, theindividual components can be mixed with one another before incorporationinto the polymer for example by dry blending, compaction or in the melt.

The incorporation of the triblock-copolymer or grafted comb copolymer ofthe invention and optional further components into the polymer iscarried out by known methods such as dry blending in the form of apowder, or wet mixing in the form of solutions, dispersions orsuspensions for example in an inert solvent, water or oil. The additivesof the invention and optional further additives may be incorporated, forexample, before or after molding or also by applying the dissolved ordispersed additve or additive mixture to the polymer material, with orwithout subsequent evaporation of the solvent or thesuspension/dispersion agent. They may be added directly into theprocessing apparatus (e.g. extruders, internal mixers, etc), e.g. as adry mixture or powder or as solution or dispersion or suspension ormelt.

The incorporation can be carried out in any heatable container equippedwith a stirrer, e.g. in a closed apparatus such as a kneader, mixer orstirred vessel. The incorporation is preferably carried out in anextruder or in a kneader. It is immaterial whether processing takesplace in an inert atmosphere or in the presence of oxygen.

The addition of the additive or additive blend to the polymer can becarried out in all customary mixing machines in which the polymer ismelted and mixed with the additives. Suitable machines are known tothose skilled in the art. They are predominantly mixers, kneaders andextruders.

The process is preferably carried out in an extruder by introducing theadditive during processing.

Particularly preferred processing machines are single-screw extruders,contrarotating and corotating twin-screw extruders, planetary-gearextruders, ring extruders or cokneaders. It is also possible to useprocessing machines provided with at least one gas removal compartmentto which a vacuum can be applied.

Suitable extruders and kneaders are described, for example, in Handbuchder Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W.Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4 (Vol. 2Extrusionsanlagen 1986, ISBN 3-446-14329-7).

For example, the screw length is 1-60 screw diameters, preferably 35-48screw diameters. The rotational speed of the screw is preferably 10-600rotations per minute (rpm), very particularly preferably 25-300 rpm.

The maximum throughput is dependent on the screw diameter, therotational speed and the driving force. The process of the presentinvention can also be carried out at a level lower than maximumthroughput by varying the parameters mentioned or employing weighingmachines delivering dosage amounts.

If a plurality of components are added, these can be premixed or addedindividually.

The triblock-copolymer or grafted comb copolymer of the invention andoptional further additives can also be added to the polymer in the formof a masterbatch (“concentrate”) which contains the components in aconcentration of, for example, about 1% to about 40% and preferably 2%to about 20% by weight incorporated in a polymer. The polymer must notbe necessarily of identical structure than the polymer where theadditives are added finally. In such operations, the polymer can be usedin the form of powder, granules, solutions, suspensions or in the formof latices.

Incorporation can take place prior to or during the shaping operation,or by applying the dissolved or dispersed compound to the polymer, withor without subsequent evaporation of the solvent.

The materials containing the triblock-copolymer or grafted combcopolymer of the invention described herein can be used for theproduction of moldings, rotomolded articles, injection molded articles,blow molded articles, films, tapes, mono-filaments, fibers, nonwovens,profiles, adhesives or putties, surface coatings and the like.

The triblock-copolymer can be prepared according to standardpolymerization methods, such as for example anionic polymerization ofthe individual blocks. Such a method is for example described fordiblock-copolymers of polyethylene and polysiloxane in U.S. Pat. No.6,331,589.

The synthesis of triblock copolymers via anionic polymerization is wellknown and e.g. described in Houben-Weyl, Methoden der organischenChemie, Band E20, page 132, Stuttgart 1987.

Synthesis can be performed either in a 3 step process, where the firstmonomer, is initiated e.g. by 2-butyllithium (block B), followed byaddition of the 2^(nd) monomer (resulting in B-C block) and finally thefirst monomer is added again (resulting in B-C-B). A 2 step process isachieved by using a bifunctional initiator e.g. Naphthalin sodium THFcomplex, where the block C is synthesized first, followed by addition ofthe second monomer, whereas both B blocks are formed at the same time. Afurther possibility of a 2 step process is the initiation of the firstmonomer by a monofunctional initiator, followed by the second monomerand coupling of the living chain ends by addition of a coupling agente.g. α,ω-dichlorocompounds or dichlordimethylsilane. Comb polymers viaanionic polymerization can be synthesized by metalization of a polymerchain e.g. polybutadiene with butyl-lithium-1,2-bis(dimethylamino)ethancomplex, followed by initiation of the second monomer from the metal(Li) containing polymer backbone.

A further method to synthesize the B-C-B block copolymers is bycondensation reaction between functional endgroups of indiviual blocks.For example a dimethyl-amino-terminated polysiloxane at both ends (blockC) can be reacted with a hydroxy-terminated block B by condensationreaction (see e.g. Houben Weyl Vol. 20 E, page 2232).

In a preferred method the block polymerization is carried out in thepresence of nitroxyl mediated radical polymerization in a similar way asdescribed for diblocks in Polymer Preprints Vol 40(2), 1999, pages370-371.

The synthesis of B-C blockcopolymers via nitroxyl mediatedpolymerization is carried out as described e.g. in WO 02/48205.

Synthesis of B-C-B blockcopolymers via nitroxyl mediated polymerizationcan be synthesized by subsequent block copolymer formation, startingwith a monomer B, followed by a monomer C and again followed by amonomer B. Another possibility is to use a bifunctionalnitroxylinitiator as described for example in U.S. Pat. No. 5,627,248,polymerizing first a monomer C, followed by the monomer B which is inthis case growing on both ends, resulting in a B-C-B structure.

A further aspect of the invention is therefore a process for thepreparation of a triblock-copolymer or graft-copolymer via controlledfree radical polymerization comprising the steps of

-   -   a) reacting a polysiloxane, in the presence of a functional        alkoxyamine of formula (I)

-   -    under hydrosylilation conditions and    -   b) reacting the resulting alkoxyamine terminated polysiloxane        with an ethylenically unsaturated monomer at a temperature        between 60 and 160° C., wherein    -   X represents a group having at least one carbon atom and is such        that the free radical

-   -    is capable of initiating polymerization of ethylenically        unsaturated monomers,    -   n is a number from 0-18;        -   R and R′ are independently tertiary bound C₄-C₂₈alkyl groups            which are unsubstituted or substitituted by one or more            electron withdrawing groups or by phenyl; or        -   R and R′ together form a 5 or 6 membered heterocyclic ring            which is substituted at least by 4 C₁-C₄alkyl groups and            which may be interrupted by a further nitrogen or oxygen            atom.

Suitable nitroxyl radicals as precursors for the compounds of formula Iare known and disclosed in the following documents.

U.S. Pat. No. 5,322,912 to Georges et al. issued Jun. 21, 1994 disclosesa polymerization process using a free radical initiator, a polymerizablemonomer compound and a stable free radical agent of the basic structureR′R″N—O● for the synthesis of homopolymers and block copolymers whichare terminated by the nitroxyl radical.

More recently further nitroxyl radicals and nitroxyl ethers have beendescribed. WO 98/13392 for example describes open chain alkoxyaminecompounds, which have a symmetrical substitution pattern and are derivedfrom NO gas or from nitroso compounds.

WO 96/24620 describes a polymerization process in which very specificstable free radical agents are used, such as for example

WO 98/30601 discloses specific nitroxyls based on imidazolidinons.

WO 98/44008 discloses specific nitroxyls based on morpholinones,piperazinones and piperazindiones.

The preparation of open chain nitroxyl radicals is for example alsodescribed in WO 99/03894 or in WO 00/07981. Nitroxyl radicals based ontetraalkyl piperidine are for example described in GB 2 335 1290 or inGB 2 361 235. Further heterocyclic nitroxyl radicals are described in GB2 342 649.

These prior art nitroxyl radicals are all suitable precursors for theinstant functional alkoxyamines. They may be prepared in analogy to theepoxy functionalized alkoxyamines disclosed in WO 02/48109.

In principal a hydroxy functional alkoxyamine is reacted with a halogenalkene having the double bond as terminal group, such as for exampleallyl bromide.

Preferably the functional alkoxyamine is of formula (II)

wherein

Y is a direct bond, O, NH, C(O)O or S;

n is a a number from 0-18.

R₁, R₂, R₃ and R₄ are independently of each other C₁-C₄alkyl;

R₅ is hydrogen or C₁-C₄alkyl;

R′₆ is hydrogen and R₆ is H, OR₁₀, NR₁₀R₁₁, —O—C(O)—R₁₀ orNR₁₁—C(O)—R₁₀;

R₁₀ and R₁₁ independently are hydrogen, C₁-C₁₈alkyl, C₂-C₁₈alkenyl,C₂-C₁₈alkinyl or C₂-C₁₈alkyl which is substituted by at least onehydroxy group or, if R₆ is NR₁₀R₁₁, taken together, form aC₂-C₁₂alkylene bridge or a C₂-C₁₂-alkylene bridge interrupted by atleast one O atom; or

R₆ and R′₆ together are both hydrogen, a group ═O or ═N—O—R₂₀ wherein

R₂₀ is H, straight or branched C₁-C₁₈alkyl, C₃-C₁₈alkenyl orC₃-C₁₈alkinyl, which may be unsubstituted or substitued, by one or moreOH, C₁-C₈alkoxy, carboxy, C₁-C₈alkoxycarbonyl;

C₅-C₁₂cycloalkyl or C₅-C₁₂cycloalkenyl;

phenyl, C₇-C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁-C₈alkyl, halogen, OH, C₁-C₈alkoxy,carboxy, C₁-C₈alkoxycarbonyl;

—C(O)—C₁-C₃₆alkyl, or an acyl moiety of a α,β-unsaturated carboxylicacid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having7 to 15 carbon atoms;

—SO₃ ⁻Q⁺, —PO(O⁻Q⁺)₂, —P(O)(OR₂)₂, —SO₂)₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂,or Si(Me)₃, wherein Q⁺ is H⁺, ammonium or an alkali metal cation; or

R₆ and R₆′ are independently —O—C₁-C₁₂alkyl, —O—C₃-C₁₂alkenyl,—O—C₃-C₁₂alkinyl, —O—C₅-C₈cycloalkyl, —O-phenyl, —O-naphthyl,—O—C₇-C₉phenylalkyl; or

R₆ and R′₆ together form one of the bivalent groups—O—C(R₂₁)(R₂₂)—CH(R₂₃)—O—, —O—CH(R₂₁)—CH₂₂—C(R₂₂)(R₂₃)—O—,—O—CH(R₂₂)—CH₂—C(R₂₁)(R₂₃)—O—, —O—CH₂—C(R₂₁)(R₂₂)—CH(R₂₃)—O—,—O-o-phenylene-O—, —O—-1,2-cyclohexyliden-O—,

R₂₁ is hydrogen, C₁-C₁₂alkyl, COOH, COO—(C₁-C₁₂)alkyl or CH₂OR₂₄;

R₂₂ and R₂₃ are independently hydrogen, methyl ethyl, COOH orCOO—(C₁-C₁₂)alkyl; and

R₂₄ is hydrogen, C₁-C₁₂alkyl, benzyl, or a monovalent acyl residuederived from an aliphatic, cycloaliphatic or aromatic monocarboxylicacid having up to 18 carbon atoms.

Preferably Y is O and n is a number from 1-4.

C₁-C₁₈alkyl can be linear or branched. Examples are methyl, ethyl,propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl,hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl,dodecyl or octadecyl. Where up to C₃₋₆alkyl is possible, C₁-C₁₈alkyl ispreferred. Alkyl substituted by a group —COOH is for example CH₂—COOH,CH₂—CH₂—COOH, (CH₂)₃—COOH or CH₂—CHCOOH—CH₂—CH₃

Hydroxyl- or alkoxycarbonyl substituted C₁-C₁₈alkyl can be, for example,2-hydroxyethyl, 2-hydroxypropyl, methoxycarbonylmethyl or2-ethoxycarbonylethyl.

Alkenyl having from 2 to 18 carbon atoms is a branched or unbranchedradical, for example propenyl, 2-butenyl, 3-butenyl, isobutenyl,n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl,isododecenyl.

Alkinyl having from 2 to 18 carbon atoms is a branched or unbranchedradical, for example propinyl, 2-butinyl, 3-butinyl, isobutinyl,n-2,4-pentadiinyl, 3-methyl-2-butinyl, n-2-octinyl, n-2-dodecinyl,isododecinyl.

Examples of alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy,isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy or octoxy.

C₇-C₉phenylalkyl is for example benzyl, α-methylbenzyl,α,α-dimethylbenzyl or 2-phenylethyl, benzyl is preferred.

C₅-C₁₂cycloalkyl is for example cyclopentyl, cyclohexyl, cycloheptyl,methylcyclopentyl or cyclooctyl.

C₅-C₁₂cycloalkenyl is for example 3-cyclopentenyl, 3-cyclohexenyl or3-cycloheptenyl.

Examples of a monocarboxylic acid having up to 18 carbon atoms areformic acid, acetic acid, propionic acid, the isomers of valeric acid,methyl ethyl acetic acid, trimethyl acetic acid, capronic acid, lauricacid or stearic acid. Examples for unsaturated aliphatic acids areacrylic acid, methacrylic acid, crotonic acid, linolic acid and oleicacid.

Typical examples of cycloaliphatic carboxylic acids are cyclohexanecarboxylic acid or cyclopentane carboxylic acid.

Examples of aromatic carboxylic acids are benzoic acid, salicylic acidor cinnamic acid. Halogen is F, Cl, Br or I.

C₁-C₁₈alkylene is a branched or unbranched radical, for examplemethylene, ethylene, propylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, heptamethylene, octamethylene,decamethylene or dodecamethylene.

C₂-C₁₂alkylene bridges interrupted by at least one O atom are, forexample, —CH₂—O—CH₂—CH₂, —CH₂—O—CH₂—CH₂—CH₂, —CH₂—O—CH₂—CH₂—CH₂—CH₂—,—CH₂—O—CH₂—CH₂—O—CH₂—.

Alkoxycarbonyl is for example methoxycarbonyl, ethoxycarbonyl,propoxycarbonyl.

Preferably R₁, R₂, R₃, R₄ are methyl, or R₁ and R₃ are ethyl and R₂ andR₄ are methyl, or R₁ and R₂ are ethyl and R₃ and R₄ are methyl.

For instance R₅ is hydrogen or methyl.

In particular R′₆ is hydrogen and R₆ is H, OR₁₀, NR₁₀R₁₁, —O—C(O)—R₁₀ orNR₁₁—C(O)—R₁₀;

R₁₀ and R₁₁ independently are hydrogen, C₁-C₁₈alkyl, C₂-C₁₈alkenyl,C₂-C₁₈alkinyl or C₂-C₁₈alkyl which is substituted by at least onehydroxy group or, if R₆ is NR₁₀R₁₁, taken together, form aC₂-C₁₂alkylene bridge or a C₂-C₁₂-alkylene bridge interrupted by atleast one O atom; or

R₆ and R′₆ together are both hydrogen, a group ═O or ═N—O—R₂₀ whereinR₂₀ is H or straight or branched C₁-C₁₈alkyl.

In another preferred embodiment of the invention R₆ and R′₆ togetherform one of the bivalent groups —O—C(R₂₁)(R₂₂)—CH(R₂₃)—O—,—O—CH(R₂₁)—CH₂₂—C(R₂₂)(R₂₃)—O—, —O—CH(R₂₂)—CH₂—C(R₂₁)(R₂₃)—O—,—O—CH₂—C(R₂₁)(R₂₂)—CH(R₂₃)—O— and R₂₁, R₂₂ and R₂₃ have the meaning asdefined above.

In a first step a polysiloxane is prepared, for example by ring openingof a cyclic siloxane.

Polysiloxanes with hydrogen end groups or with pending hydrogen atoms atthe polymer backbone are known and commercially available. Methods forreacting hydrogen groups with unsaturated double bonds are known ashydrosililation and for example described in Advances in OrganometallicChemistry, vol. 17 pages 407-447, 1979.

During the hydrosylilation process an alkoxyamine having for example anallyl functionality in particular a compound of formula II, is added anda polysiloxane having attached the alkoxyamine at both ends or along thepolysiloxane backbone is obtained. Depending on the process conditionsand the amount of alkoxyamine added, comb polymers with more than twopendent alkoxyamine groups are obtained.

In a second step the alkoxyamine terminated polysiloxane is furtherreacted with an unsaturated monomer. Examples of unsaturated monomersare ethylene, propylene, n-butylene, i-butylene, styrene, substitutedstyrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone,vinylimidazole, maleic anhydride, (alkyl)acrylic acidanhydrides,(alkyl)acrylic acid salts, (alkyl)acrylic esters, (meth)acrylonitriles,(alkyl)acrylamides, vinyl halides or vinylidene halides.

Preferred ethylenically unsaturated monomers are styrene,methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert.butylacrylate, hydroxyethylacrylate, hydroxypropylacrylate,dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,glycidyl(meth)acrylates, acrylonitrile, acrylamide, methacrylamide ordimethylaminopropyl-methacrylamide.

Particularly preferred are styrene, methylacrylate, ethylacrylate,butylacrylate, isobutylacrylate, tert. butylacrylate,methyl(meth)acrylate, ethyl(meth)acrylate and the isomers ofbutyl(meth)acryl ate.

Also subject of the invention is the triblock-copolymer orgraft-copolymer itself obtained via controlled free radicalpolymerization according to the above mentioned process.

The compounds of formula II are novel. They may be prepared in analogyto the epoxy-functional compounds described in WO 99/46261, WO 02/48109or U.S. Pat. No. 5,721,320. The hydroxy functional intermediatedescribed in the afore mentioned documents is for example reacted withallyl bromide to obtain the title compounds.

Consequently a further aspect of the invention is a compound of formulaII

wherein

Y is a direct bond, O, NH, C(O)O or S;

n is a a number from 0-18.

R₁, R₂, R₃ and R₄ are independently of each other C₁-C₄alkyl;

R₅ is hydrogen or C₁-C₄alkyl;

R′₆ is hydrogen and R₆ is H, OR₁₀, NR₁₀R₁₁, —O—C(O)—R₁₀ orNR₁₁—C(O)—R₁₀;

R₁₀ and R₁₁, independently are hydrogen, C₁-C₁₈alkyl, C₂-C₁₈alkenyl,C₂-C₁₈alkinyl, or C₂-C₁₈alkyl which is substituted by at least onehydroxy group or, if R₆ is NR₁₀R₁₁, taken together, form aC₂-C₁₂alkylene bridge or a C₂-C₁₂-alkylene bridge interrupted by atleast one O atom; or

R₆ and R′₆ together are both hydrogen, a group ═O or ═N—O—R₂₀ whereinR₂₀ is H, straight or branched C₁-C₁₆alkyl, C₃-C₁₈alkenyl orC₃-C₁₈alkinyl, which may be unsubstituted or substitued, by one or moreOH, C₁-C₈alkoxy, carboxy, C₁-C₈alkoxycarbonyl;

C₅-C₁₂cycloalkyl or C₅-C₁₂cycloalkenyl;

phenyl, C₇-C₉phenylalkyl or naphthyl which may be unsubstituted orsubstituted by one or more C₁-C₈alkyl, halogen, OH, C₁-C₈alkoxy,carboxy, C₁-C₈alkoxycarbonyl;

—C(O)—C₁-C₃₆alkyl, or an acyl moiety of a α,β-unsaturated carboxylicacid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having7 to 15 carbon atoms;

—SO₃ ⁻Q⁺, —PO(O⁻Q₊)₂, —P(O)(OR₂)₂, —SO₂—R₂, —CO—NH—R₂, —CONH₂, COOR₂, orSi(Me)₃, wherein Q⁺ is H⁺, ammnonium or an alkali metal cation; or

R₆ and R₆′ are independently —O—C₁-C₁₂alkyl, —O—C₃-C₁₂alkenyl,—O—C₃-C₁₂alkinyl, —O—C₅-C₈cycloalkyl, —O-phenyl, —O-naphthyl,—O—C₇-C₉phenylalkyl; or

R₆ and R′₆ together form one of the bivalent groups—O—C(R₂₁)(R₂₂)—CH(R₂₃)—O—, —O—CH(R₂₁)—CH₂₂—C(R₂₂)(R₂₃)—O—,—O—CH(R₂₂)—CH₂—C(R₂₁)(R₂₃)—O—, —O—CH₂—C(R₂₁)(R₂₂)—CH(R₂₃)—O—,—O-o-phenylene-O—, —O-1,2-cyclohexyliden-O—,

R₂₁ is hydrogen, C₁-C₁₂alkyl, COOH, COO—(C₁-C₁₂)alkyl or CH₂OR₂₄;

R₂₂ and R₂₃ are independently hydrogen, methyl ethyl, COOH orCOO—(C₁-C₁₂)alkyl; and

R₂₄ is hydrogen, C₁-C₁₂alkyl, benzyl, or a monovalent acyl residuederived from an aliphatic, cycloaliphatic or aromatic monocarboxylicacid having up to 18 carbon atoms.

Examples and preferences for the individual substituents have alreadybeen given, they apply also for the compounds.

Yet further aspects of the invention are a composition wherein thetriblock-copolymer or graft-copolymer is prepared via controlled freeradical polymerization according to the process described above and theuse of a triblock-copolymer or graft graft-copolymer as additive forenhancing the melt flow of thermoplastic polymers during processing.

The following examples illustrate the invention.

A) Synthesis of Functional Alkoxyamine

EXAMPLE 1 Compound 101

15 g (51 mmol)1-[1-(4-hydroxy-phenyl)-ethoxy]-2,2,6,6-tetramethyl-piperidin-4-olprepared as described in WO 02/48109, 14 g (102 mmol) K₂CO₃, 8.6 ml (102mmol) allylbromide and 50 ml acetone are refluxed for 12 hours. Thereaction mixture is filtered and the solvent removed by evaporation. Theresidue is recrystallized from 20 ml pentane. 11.3 g (66.4%) of compound101 are obtained as white crystals with a melting point of 66-67° C.

Compound No. Structure 101

Elemental Analysis: Calculated C₂₀H₃₁NO₃; C, 72.03%; H, 9.37%; N, 4.20%;Found: C, 71.46%; H, 9.36%; N, 4.27%.

B) Synthesis of the NOR Terminated Polysiloxane

Two commercial Polysiloxane are modified in a hydrosylilation reactionin the presence of compound 101. A NOR terminated polysiloxane of thetype B-C-B and a grafted polysiloxane of the type C-B(n) is obtained.

C) Synthesis of Block Copolymer B-C-B of Example 1 to 4

In a dry, argon-purged Schienk tube, the NOR terminated polysiloxane isdissolved in a tenfold amount of freshly distilled styrene. The solutionis degassed in three consecutive freeze-thaw-cycles and then purged withArgon. The stirred mixture is immersed in an oil bath and polymerized at130° C. for 24 hours. After polymerization, residual monomer is removedunder vacuum at 60° C. The final block copolymer is dried at 60° C. invacuum until constant weight is achieved.

Molecular weight and molecular weight distributions are determined bysize exclusion chromatography (SEC) on an HP 1090 liquid chromatograph(software: winGPC/Polymer Standard Services, Mainz, Germany) using THFas eluent and a column combination calibrated with narrow polystyrenestandards (Polymer Laboratories). The results are shown in Table 1.

TABLE 1 blockcopolymer styrene conv. of example starting material [g][g] [%] M_(w) PD PS-PSi-PS (ex. 1, 3) NO-term- 5.0 50 67.6 7100 4.8polysiloxane PS-graft-PSi NO-graft- 5.0 50 53.1 8000 1.7 (ex. 2, 4)polysiloxane

Processing and Testing Conditions

The synthesized block copolymers described above are blended withcrystal polystyrene and injection molded to a spiral (dimension: 1.5 mm)where the length of the spiral is used as measure of flowability. Inaddition the transparency of the injection molded spirals is inspectedvisually. The results of improved melt flow and transparency of theinventive examples are listed in Table 2.

Arburg 270-210-500 Cylinder Temp. Zone: 200–220° C. Temp. Dye: 220° C.Mould Temperature: 55° C. Mould Cooling Time: 10 sec. Injection Time:0.1–0.2 sec. Screw Speed: 150 U/min Back Pressure: 55 bar Back PressureTime: 10 sec. Injection Pressure: 1000 bar

TABLE 2 melt flow increase additive [%] [%] aspect comparative without 00   transparent, colorless example 1 comparative Tegomer ® v-si 2250 1.05.3 white, opaque, example 2 inhomogeneous comparative Tegomer ® h-si6440 1.0 0.3 white, opaque example 3 comparative polysiloxane block of1.0 3.2 opaque, brownish example 4 example 1 comparative polysiloxaneblock of 1.0 not example 5 example 2 processible comparative Tegomer ®h-si 6440 2.0 7.7 white, opaque example 6 comparative Tegomer ® v-si2250 2.0 5.0 white, opaque, example 7 inhomogeneous example 1ps-polysiloxane-ps 1.0 1.2 transparent colorless blockcopolymer example2 polysiloxane-graft-ps 1.0 5.0 transparent colorless example 3ps-polysiloxane-ps 2.0 3.2 transparent colorless blockcopolymer example4 polysiloxane-graft-ps 2.0 6.2 transparent colorless

In contrast to commercial available Polysiloxanes of the comparativeexamples, the inventive examples show enhancement of melt flow and atthe same time excellent compatibility proven by a colorless transparentproduct. Glass tranistion temperature of PS is 373 K, ofPolydimethylsiloxane 146 K

1. A composition comprising A) a thermoplastic polymer and B1) a triblock-copolymer of the formula B-C-B; or B2) a graft copolymer wherein a polymer block B is grafted onto a polymer C to form a comb copolymer of idealized formula C-B(n) wherein n is greater than 2; wherein the polymer block B is compatible to the thermoplastic polymer A); and the polymer block C is a polysiloxane which has a glass transition temperature of at least 20° K. below the glass transition temperature of the thermoplastic polymer A); and the average molecular weight M_(w) of the triblock-copolymer B1) or grafted comb copolymer B2) is below 50 000, and wherein the triblock copolymer or the graft copolymer is prepared via controlled free radical polymerization comprising the steps a) reacting a polysiloxane, in the presence of a functional alkoxyamine of formula (I)

 under hydrosylilation conditions and b) reacting the resulting alkoxyamine modified polysiloxane with an ethylenically unsaturated monomer at a temperature between 60 and 160° C., wherein X represents a group having at least one carbon atom and is such that the free radical

 is capable of initiating polymerization of ethylenically unsaturated monomers, n is a number from 0-18; R and R′ are independently tertiary bound C₄-C₂₈alkyl groups which are unsubstituted or substitituted by one or more electron withdrawing groups or by phenyl; or R and R′ together form a 5 or 6 membered heterocyclic ring which is substituted at least by 4 C₁-C₄alkyl groups and which may be interrupted by a further nitrogen or oxygen atom.
 2. A composition according to claim 1 wherein the thermoplastic polymer A is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyacrylate, polymethacrylate, polyvinylchloride, polyphenyleneoxide, polyvinylacetate, polyamide and polyester.
 3. A composition according to claim 1 wherein the polymer block B is selected from the group consisting of polyisoprene, polybutadiene, polystyrene polymethacrylate and polyacrylate.
 4. A composition according to claim 1 wherein the thermoplastic polymer A and the triblock-copolymer B-C-B are polystyrene polystyrene-polysiloxane-polystyrerie, polyethylene polyisoprene-polysiloxane-polyisoprene, polypropylene polyisoprene-polysiloxane-polyisoprene, polymethylmethacrylate polymethylacrylate-polysiloxane-polymethylacrylate, polyamide polyethylacrylate-polysiloxane-polyethylacrylate, polyester polyethylacrylate-polysiloxane-polyethylacrylate, polyvinylchloride polyethylacrylate-polysiloxane-polyethylacrylate, polyvinylchloride poly-n-butylacrylate-polysiloxane-poly-n-butylacrylate, polyphenyleneoxide polystyrene-polysiloxane-polystyrene or polyvinylacetate polymethylacrylate-polysiloxane-polymethylacrylate.
 5. A composition according to claim 1 wherein the glass transition temperature of the polymer block C is 50° K. below the glass transition temperature of the thermoplastic polymer A.
 6. A composition according to claim 1 wherein the average molecular weight M_(w) of the triblock-copolymer or graft-copolymer is below
 30000. 7. A composition according to claim 1 wherein the triblock-copolymer or graft copolymer is present in an amount of from 0.1 to 10% by weight, based on the weight of the thermoplastic polymer A.
 8. A process for enhancing the melt flow of a thermoplastic polymer during processing, which process comprises adding a triblock-copolymer or graft copolymer according to claim 1 to a thermoplastic polymer and processing the polymer. 